可控碳改性Pd/TiO<sub>2</sub>用于直接合成双氧水:非均相界面对催化性能的影响

引用本文: 严伟, 孙睿, 李蒙, 李力成, 杨祝红, 花泽林, 陆小华, 刘畅. 可控碳改性Pd/TiO₂用于直接合成双氧水:非均相界面对催化性能的影响[J]. 催化学报, 2020, 41(2): 312-321. doi: S1872-2067(19)63412-1 shu

Citation: Wei Yan, Rui Sun, Meng Li, Licheng Li, Zhuhong Yang, Zelin Hua, Xiaohua Lu, Chang Liu. Heterogeneous interfacial engineering of Pd/TiO₂ with controllable carbon content for improved direct synthesis efficiency of H₂O₂[J]. Chinese Journal of Catalysis, 2020, 41(2): 312-321. doi: S1872-2067(19)63412-1 shu

可控碳改性Pd/TiO₂用于直接合成双氧水:非均相界面对催化性能的影响

严伟 ^a, ,
孙睿 ^a, ,
李蒙 ^a, ,
李力成 ^b, ,
杨祝红 ^a, ,
花泽林 ^b, ,
陆小华 ^a, ,
刘畅 ^a,

a 南京工业大学化学工程学院, 材料化学工程国家重点实验室, 江苏南京 210009;
b 南京林业大学化学工程学院, 木质纤维素功能材料创新研究中心, 江苏南京 210037
基金项目:
国家自然科学基金（21878143，21476106，21838004）；海外及港澳学者合作研究基金（21729601）；材料化学工程国家重点实验室基金（ZK201702）；江苏省高等学校重点学科建设（PAPD）.

摘要: 双氧水（H₂O₂）是一种重要的绿色氧化剂，广泛应用于纺织、医疗、废水处理、军事等重要领域.目前，H₂O₂的工业生产以蒽醌法为主，该法设备投资大、运行成本高，同时工艺涉及大量的有机溶液，活性中间体蒽醌也会发生缓慢降解，产生有毒副产物.与蒽醌法相比，通过负载型贵金属催化剂催化H₂与O₂反应直接合成H₂O₂，过程绿色环保且生产工艺简单，引起了各界广泛关注.然而，从热力学上分析，H₂和O₂更容易反应生成H₂O，H₂O₂只是该反应的中间产物，会继续发生加氢和直接分解反应生成H₂O，导致H₂和O₂的低效利用，开发高H₂O₂选择性且高反应效率的催化剂已成为氢氧直接合成H₂O₂研究的重点与难点.目前大部分研究策略旨在通过调控或影响反应中心结构、价态来抑制H₂O₂的副反应，进而提升H₂O₂的选择性和反应效率；尽管已取得了良好的进展，但仍需发展新的调控策略来满足工业应用的要求.
本课题组前期研究表明，促使H₂O₂从催化剂上脱附可以有效地提升H₂O₂的选择性和产率.相比于针对反应中心的调控，不稳定的H₂O₂从催化剂上快速脱附同样起到抑制H₂O₂参与副反应的作用.为此，本文提出一种炭量可控的非均一界面改性方法，以常规的Pd/TiO₂作为研究对象，借助各种结构表征，发现炭物种在TiO₂表面呈非均一分散状态，而且改性对于催化剂的几何结构影响较小；另外，催化剂表面的疏水性会随着碳含量的增加而增加，导致其与H₂O₂间的吸附能相应变小.反应结果显示，表面非均一的炭化改性技术可以显著提升Pd/TiO₂催化剂的H₂O₂选择性和产率.通过构效关系分析，可知这种改性技术可以保持Pd颗粒与TiO₂间相互作用的同时，还可以促进H₂O₂的快速脱附，进而提升改性Pd/TiO₂催化剂的H₂O₂直接合成效率.该改性方法简单、易控，可拓展应用到其他类型催化剂的H₂O₂直接合成性能调控与改进.

关键词:

English

Heterogeneous interfacial engineering of Pd/TiO₂ with controllable carbon content for improved direct synthesis efficiency of H₂O₂

a State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China;
b College of Chemical Engineering, Innovation Research Center of Lignocellulosic Functional Materials, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
Received Date: 28 March 2019
Revised Date: 22 May 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21878143, 21476106, 21838004), Joint Re-search Fund for Overseas Chinese Scholars and Scholars in Hong Kong and Macao Young Scholars (21729601), the fund of State Key Laboratory of Materials-Oriented Chemical Engineering (ZK201702), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

Abstract: Series of heterogeneous interfacial engineered TiO₂ (C-TiO₂) with controllable carbon content were facilely synthesized by incipient-wet impregnation using glucose and subsequent thermal carbonization. The obtained C-TiO₂ were used as catalytic supports to load Pd nanoparticles for H₂O₂ direct synthesis from H₂ and O₂. The as-prepared samples were systematically studied by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), air isothermal microcalorimeter, temperature-programmed reduction of H₂ (H₂-TPR), and so on. The catalytic results showed that H₂O₂ productivity and H₂O₂ selectivity of Pd/C-TiO₂ firstly rose with increasing carbon content and then declined. Pd/C-TiO₂ catalyst with 1.89 wt% of carbon content showed the best catalytic performance that had 61.2% of selectivity and 2192 mmol H₂O₂/g_Pd/h of productivity, which were significantly better than those of pristine Pd/TiO₂ (45.2% and 1827 mmol H₂O₂/g_Pd/h). Various characterization results displayed that the carbon species were heterogeneously dispersed on TiO₂ surface. Moreover, no obvious geometric transformation in supports and Pd nanoparticles were observed among different catalysts. The superficial hydrophobicity of Pd/C-TiO₂ was gradually promoted with increasing carbon content, which led to the corresponding decrease in adsorption energy of H₂O₂ with catalysts. According to structure-performance relationship analyses, the heterogeneous interfacial engineering of carbon could maintain the interaction of Pd nanoparticles with TiO₂ and simultaneously accelerate the H₂O₂ desorption. Both factors further determined the excellent H₂O₂ direct synthesis performance of Pd/C-TiO₂.

Key words:

1. [1] X. S. Chai, Q. X. Hou, Q. Luo, J. Y. Zhu, Anal. Chim. Acta., 2004, 507, 281-284.
2. [2] J. M. Campos-Martin, G. Blanco-Brieva, J. L. Fierro, Angew. Chem. Int. Ed., 2006, 45, 6962-6984.
3. [3] J. K. Edwards, S. J. Freakley, A. F. Carley, C. J. Kiely, G. J. Hutchings, Acc. Chem. Res., 2013, 47, 845-854.
4. [4] S. Ranganathan, V. Sieber, Catalysts, 2018, 8, 379/1-379/22.
5. [5] P. F. Tian, L. Ouyang, X. C. Xu, J. Xu, Y. F. Han, Chin. J. Catal., 2013, 34, 1002-1012.
6. [6] J. K. Edwards, S. J. Freakley, R. J. Lewis, J. C. Pritchard, G. J. Hutchings, Catal. Today, 2015, 248, 3-9.
7. [7] Y. Yi, L. Wang, G. Li, H. C. Guo, Catal. Sci. Technol., 2016, 6, 1593-1610.
8. [8] L. Fu, K. T. Chuang, R. Fiedorow, Stud. Surf. Sci. Catal., 1992, 72, 33-41.
9. [9] D. Gudarzi, W. Ratchananusorn, I. Turunen, M. Heinonen, T. Salmi, Catal. Today, 2015, 248, 69-79.
10. [10] M. G. Seo, H. J. Kim, S. S. Han, K. Y. Lee, Catal. Surv. Asia., 2016, 21, 1-12.
11. [11] Y. Shao, C. Cao, S. Chen, M. He, J. Fang, J. Chen, X. Li, D. Li, Appl. Catal. B, 2015, 179, 344-351.
12. [12] D. Ding, X. Xu, P. Tian, X. Liu, J. Xu, Y. F. Han, Chin. J. Catal., 2018, 39, 673-681.
13. [13] J. K. Edwards, G. J. Hutchings, Angew. Chem. Int. Ed., 2008, 47, 9192-9198.
14. [14] J. Xu, L. Ouyang, G. J. Da, Q. Q. Song, X. J. Yang, Y. F. Han, J. Catal., 2012, 285, 74-82.
15. [15] D. Gudarzi, W. Ratchananusorn, I. Turunen, M. Heinonen, T. Salmi, Catal. Today, 2015, 248, 58-68.
16. [16] J. K. Edwards, J. Pritchard, L. Lu, M. Piccinini, G. Shaw, A. F. Carley, D. J. Morgan, C. J. Kiely, G. J. Hutchings, Angew. Chem., 2014, 53, 2381-2384.
17. [17] S. J. Freakley, Q. He, J. H. Harrhy, L. Lu, D. A. Crole, D. J. Morgan, E. N. Ntainjua, J. K. Edwards, A. F. Carley, A. Y. Borisevich, C. J. Kiely, G. J. Hutchings, Science, 2016, 351, 965-968.
18. [18] Y. Feng, Q. Shao, B. Huang, J. Zhang, X. Huang, Nat. Sci. Rev., 2018, 5, 895-906.
19. [19] J. Zhang, Q. Shao, Y. Zhang, S. Bai, Y. Feng, X. Huang, Small, 2018, 14, 1703990.
20. [20] S. Park, T. J. Kim, Y. M. Chung, S. H. Oh, I. K. Song, Catal. Lett., 2009, 130, 296-300.
21. [21] S. Park, S. H. Baeck, T. J. Kim, Y. M. Chung, S. H. Oh, I. K. Song, J. Mol. Catal. A, 2010, 319, 98-107.
22. [22] Y. F. He, J. T. Feng, Y. Y. Du, D. Q. Li, ACS Catal., 2012, 2, 1703-1710.
23. [23] J. Kim, Y. M. Chung, S. M. Kang, C. H. Choi, B. Y. Kim, Y. T. Kwon, T. J. Kim, S. H. Oh, C. S. Lee, ACS Catal., 2012, 2, 1042-1048.
24. [24] J. K. Edwards, E. Ntainjua, A. F. Carley, A. A. Herzing, C. J. Kiely, G. J. Hutchings, Angew. Chem. Int. Ed., 2009, 48, 8512-8515.
25. [25] J. K. Edwards, B. Solsona, E. Ntainjua N, A. F. Carley, A. A. Herzing, C. J. Kiely, G. J. Hutchings, Science, 2009, 323, 1037-1041.
26. [26] J. K. Edwards, J. Pritchard, M. Piccinini, G. Shaw, Q. He, A. F. Carley, C. J. Kiely, G. J. Hutchings, J. Catal., 2012, 292, 227-238.
27. [27] J. K. Edwards, S. F. Parker, J. Pritchard, M. Piccinini, S. J. Freakley, Q. He, A. F. Carley, C. J. Kiely, G. J. Hutchings, Catal. Sci. Technol., 2013, 3, 812-818.
28. [28] J. Li, T. Ishihara, K. Yoshizawa, J. Phys. Chem. C, 2011, 115, 25359-25367.
29. [29] J. Li, A. Staykov, T. Ishihara, K. Yoshizawa, J. Phys. Chem. C, 2011, 115, 7392-7398.
30. [30] R. Tu, S. Y. Chen, W. Cao, S. Y. Zhang, L. C. Li, T. Ji, J. H. Zhu, J. Li, X. H. Lu, Catal Commun., 2017, 89, 69-72.
31. [31] R. Tu, L. C. Li, S. Y. Zhang, S. Y. Chen, J. Li, X. H. Lu, Catalysts, 2017, 7, 175-183.
32. [32] L. C. Li, Y. Zhu, X. H. Lu, M. J. Wei, W. Zhuang, Z. H. Yang, X. Feng, Chem. Commun., 2012, 48, 11525-11527.
33. [33] L. C. Li, H. Q. Yue, S. Zhang, Y. Huang, W. Zhang, P. Wu, Y. Ji, F. Huo, ACS Appl. Mater. Inter., 2019, 11, 9919-9924.
34. [34] Y. F. Han, Z. Zhong, K. Ramesh, F. Chen, L. Chen, T. White, Q. Tay, S. N. Yaakub, Z. Wang, J. Phys. Chem. C, 2007, 111, 8410-8413.
35. [35] L. Ouyang, G. J. Da, P. F. Tian, T. Y. Chen, G. D. Liang, J. Xu, Y. F. Han, J. Catal., 2014, 311, 129-136.
36. [36] X. Li, Y. Z. Jiang, X. K. Li, H. X. Jiang, J. L. Liu, J. Feng, S. B. Lin, X. Guan, Rare Metals, 2016, 37, 743-749.
37. [37] Y. Bai, W. Li, C. Liu, Z. Yang, X. Feng, X. H Lu, K. Y. Chan, J. Mater. Chem., 2009, 19, 7055-7061.
38. [38] K. J. Chao, W. Y. Cheng, T. H. Yu, S. Y. Lu, Carbon, 2013, 62, 69-75.
39. [39] Y. Zhang, Z. R. Tang, X. Fu, Y. J. Xu, ACS Nano, 2010, 3, 7303-7314.
40. [40] Z. Z. Jiang, Z. B. Wang, Y. Y. Chu, D. M. Gu, G. P. Yin, Energy Environ. Sci., 2011, 4, 728-735.
41. [41] X. B. Wu, W. Zhuang, L. Lu, L. Li, J. Zhu, L. Mu, W. Li, Y. Zhu, X. Lu, Appl. Surf. Sci., 2017, 426, 890-896.
42. [42] B. Hu, W. Deng, R. Li, Q. Zhang, Y. Wang, F. Delplanque-Janssens, D. Paul, F. Desmedt, P. Miquel, J. Catal., 2014, 319, 15-26.
43. [43] L. C. Li, H. Yue, S. Chen, L. Huang, X. Li, Z. H. Yang, X. H. Lu, Catal. Lett., 2018, 148, 992-1002.
44. [44] M. Zhang, S. Liu, L. Li, X. Li, H. Huang, J. Yin, X. Shao, J. Yang, J. Energy Mater., 2016, 35, 251-264.
45. [45] L. Ouyang, P. F. Tian, G. J. Da, X. C. Xu, C. Ao, T. Y. Chen, R. Si, J. Xu, Y. F. Han, J. Catal., 2015, 321, 70-80.
46. [46] P. Tian, X. Xu, C. Ao, D. Ding, W. Li, R. Si, W. Tu, J. Xu, Y. F. Han, ChemSusChem, 2017, 10, 3342-3346.
47. [47] D. Childers, A. Saha, N. Schweitzer, R. M. Rioux, J. T. Miller, R. J. Meyer, ACS Catal., 2013, 3, 2487-2496.
48. [48] D. Zhou, L. Ding, H. Cui, H. An, J. Zhai, Q. Li, J. Power Sources, 2013, 222, 510-517.
49. [49] S. Y Chen, R. Tu, J. Li, X. H. Lu, Chin. J. Chem. Eng., 2018, 26, 534-539.
50. [50] J. K. Edwards, A. F. Carley, A. A. Herzing, C. J. Kiely, G. J. Hutchings, Faraday Discuss., 2008, 138, 225-239.
51. [51] S. Kim, D. W. Lee, K. Y. Lee, E. A. Cho, Catal. Lett., 2014, 144, 905-911.
52. [52] P. Tian, D. Ding, Y. Sun, F. Xuan, X. Xu, J. Xu, Y. F. Han, J. Catal., 2019, 369, 95-104.
53. [53] S. Chinta, J. H. Lunsford, J. Catal., 2004, 225, 249-255.
54. [54] H. Huang, X. Ye, H. Huang, L. Zhang, D. Y. C. Leung, Chem. Eng. J., 2013, 230, 73-79.
55. [55] Z. Luo, Z. Zheng, L. Li, Y. T. Cui, C. Zhao, ACS Catal., 2017, 7, 8304-8313.
56. [56] Y. Wang, J. Yang, R. Gu, L. Peng, X. Guo, N. Xue, Y. Zhu, W. Ding, ACS Catal., 2018, 8, 6419-6425.

扫一扫看文章

计量

PDF下载量: 18
文章访问数: 3407
HTML全文浏览量: 198

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

可控碳改性Pd/TiO₂用于直接合成双氧水:非均相界面对催化性能的影响

English

Heterogeneous interfacial engineering of Pd/TiO₂ with controllable carbon content for improved direct synthesis efficiency of H₂O₂

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

可控碳改性Pd/TiO2用于直接合成双氧水:非均相界面对催化性能的影响

English

Heterogeneous interfacial engineering of Pd/TiO2 with controllable carbon content for improved direct synthesis efficiency of H2O2

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

可控碳改性Pd/TiO₂用于直接合成双氧水:非均相界面对催化性能的影响

Heterogeneous interfacial engineering of Pd/TiO₂ with controllable carbon content for improved direct synthesis efficiency of H₂O₂

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs